Production of hydrocarbons



Patented June 13, 1944 2,351,24 PRODUCTION OF HYDROCARBONS Gustav Wirth, Franz Sab Leuna Germany:

klos, Property Custodian No Drawing. Application No. 330,730. In German el, and Hans Laudenvested in the Alien April 20, 1940, Serial y November 25, 1938 '4 Claims. (Cl. 260 449.6)

The present invention relates to the of hydrocarbons with pumice stone and silica gel.

In order to increase the yield of hydrocarbons with more than one carbon atom in the molecule In this operation an incomplete conversion of the mixture of carbon monoxide and hydrogen increase in output.

When working under conditions giving the optimum output of hydrocarbons with more than one carbon atom in the molecule generally also the optimum output of liquid products is obtained.

Production meters per cubic meter of catalyst and per hour give the desired results.

hen working in se W high 1; roughputs the In general the time of contact of the reaction gases in a single reaction space is more than 6 seconds, even when recycling part of the gases.

,2. 1 assum Inthe single reaction vessels the throu hput,-

nalsob ncr se bx n e m f r s a before the entry of the main gas stream into the vessel or atone or more Pointsbetween the entry and exit of the main gas stream. In this case it is not necessarythat the second and further reaction vessels are or smallersize but it is then possible to work with vesselsof-the'same size.

The gases need not pass through the second and further reaction vessels, with the same throu hput as. through the first vessel. 1 Smaller throughputs in the. subsequent vessels may even be advantageous when the composition of the gases has materially changed. Likewise the other reaction conditions, such as temperature,

pressure, catalyst activity, in the subsequent stages need not be thesameg-as or similar to h i e n the. pre iew t sse- The coolingoithe reaction vessels, which is' necessary inview oi the exothermic reaction is prererably carried out bymeans-of indirect heat hease ith 09111 8 e t h 5 1 1- under aQsuitabIe pressure or oil maybe employed. a a ddit ohal o n ma be fie d b dd ng. o h ea tive c e aldi saa' or' ampl col vdrqs n or Q erb,Qnono id r i tures thereof or acold. inert gas,

The process maybe carriedout under normal or elevated pressure, for example, a pressurebee tween 10. and 3 atmospheres, or alsounder high pre ssures, such as 100 atmospheres or more. The

reaction temperatures usually range between 150 and 350;"- C. and preferablybetween 160 and 259 C. in case catalystscontaining cobalt as, active constituent are employed. When working with iron catalysts the temperatures are usually high;

er. The process is not limited to a certain con struction ofthe conversion vessels; The usual catalysts in particular those comprising cobalt, iron and/or nickel may-be employed, for exam,-

ple, those catalysts prepared by precipitation not limited to the said examples.

Example '1 A: gasconsisting of 28'per cent of carbon monoxide, per. cent of hydrogen and percent of accompanying gases is passed under 10, at-

mospheresand-at 195 C. over a catalyst consisting of 85 parts of cobalt and 15 parts of thorium oxide 011 85 parts of diatomaceous earth in an amount of llocubic meters per cubic meter of catalyst per hour.

Thereby liquid, hydrocarbons are formed in an amount of '100 grams per c bic meter of the mixture of carbon monoxide and hydrogen: When the amount of initial gas is increased to 400 cubic meters of gas per cubic meter of catalyst per hour, the yield amounts to .gramsper cubic meter of the mixture of carbon 7 monoxide andhydrogen.

In the first ca se 9.35 kilograms of liquid prodnot are obtained per 110 cubic meters of fresh gas or per cubicmeter of catalyst, in the second case 13.6 kilograms of liquid products per 400 cubic meters of freshfgas or per cubic meter of catalyst. Therefore inthe first case an amount of per cent more of the catalyst is necessary for obtaining thesame output.

In the second case'the, gas i'reedirom the liquid productsjhas a yolume. amounting to .79 per ms m d a uch a er xa pl at in cent of. that 01 the fresh gas. It is passed with a r u ut 0 cubic me r i cubi gt l of catalyst and per hour through a second re o tion vessel, the catalyst space oi which amounts to only'79 per cent of the catalyst space ot the first vessel. In this manner a further amount ct 12 .6 kilograms of, liquid products is formed per cubic meter of catalyst. I I

The gas leaving the second vessel has a volume of only 64 per cent of that of the ireshgas, it is passed, after removal of the liquid constituents with the same throughout per cubic meter of cat alyst through a third reaction vessel, the catalyst space of whichamounts to 64 per cent oi'th t or the first vessel. Hereby a iurther amount of ii}; kilo ram iquid roduct s o m p ubi meter ofcatalyst.

T as uin mm the i d v s h s i volume of 53per cent or that oi the'ire'sh gas; it is passed, atter removal of the liquid constituents, with the same throughput per cubic meter of-catalyst through aiourthreaction vessel, the

catalystspace of which amounts to 53- per cent of that of the first vessel, Hereby a: Iurther anoin of l l wm of am rodu s s. [formed per cubic meter of catalyst.

Inthe tour vessels cont ining 2 9 6 cubic meters offcatalyst, there are obtained 36.22 kilograms of liquid products per hour whichis equivalent .to ayield of 12.2 kilograms per cubic meter or catalyst and per hour (that is 30.5 per cent more of liquid products than in the first case). For the production oi the same quantity or hydrocar bonsas in the first'case the catalyst space required inthe second case can be by zsper'cent smaller than in the first case In bcthcase the heat generated in the con; version is removed by cooling the reaction vessels by heat exchange with a cooling liquid.

Example '2 A gas containing 28per cent of carbon monoxe ide and 5'7 per cent oi hydrogen is passed at a, temperature of C. and with a, throughput of 300, cubic meters per cubic meter 01 catalyst and per hour through-a space oi'; 1.18 cubic meters filled with ,a catalyst consisting of 46 per cent of cobalt, 8 per cent of magnesium oxide and 48,

per cent of diatomac'eous earth, and, after separation of the liquid constituents formed by this treatment, through a second vessel of 1 cubic meter of internal spacewhich is filled with the same catalyst. The throughput in the second vessel is only 261.5 cubic meters or gas per cubic meter of catalyst space as compared with 300 cubic meters in the first vessel. is 10.6 kilograms of liquid products, "By addition of fresh gas before the second reaction vessel. in an amount of- 15, per cent of the gas freed from the liquid constituents coming from the first vessel the optimum throughput of 300. cubic me ters per cubic meter of catalyst space and per hour is also obtained 'in this second reaction vessel and thereby the total yield is increased I by0..6 kilogram. 1

In both cases the surplus heat. evolved in the,

- monoxide with hydrogen in a plurality of consecutive reaction -vessels with removal behind each reaction vessel of the liquid hydrocarbons The total, yield formed, the improvement of maintaining in all reaction vessels substantially the same throughput within the range from 200 to 600 cubic meters of gas per cubic meter of catalyst per hour.

2. In a process for the production of hydrocarbons having more than one carbon atom in the molecule by the catalytic conversion of carbon monoxide with hydrogen in a plurality of conseeutive reaction vessels with removal behind each reaction vessel of the liquid hydrocarbons formed, the improvement of maintaining in all the reaction vessels substantially the same throughput of gas per cubic meter of catalyst per hour by using reaction vessels of decreasing capacity, the decrease in capacity being substantially proportional to the decrease in volume of the gas supplied to each vessel.

3. In a process for the production of hydrocarbons having more than one carbon atom in the molecule by the catalytic conversion of carbon monoxide with hydrogen in a plurality of consecutive reaction vessels with removal behind each reaction vessel of the liquid hydrocarbons formed, the improvement of maintaining in all the reaction vessels substantially the same throughput within the range from 200 to 600 cubic consecutive reaction vessels with removal behindeach reaction vessel of the liquid hydrocarbons formed, the improvement of maintaining in all the reaction vessels substantially the same throughput within the range from 200 to 600 cubic meters of gas per cubic meter of catalyst per hour by adding to the gas passing into the second and subsequent vessels fresh gas in an amount substantially equal to the difference in volume of gas between that passing into the first vessel and that due to the contraction in volume by the reaction and by the removal of the produced liquid hydrocarbons from the reaction mixture leaving each vessel.

GUSTAV WIR'I'H.

FRANZ SABEL.

HANS LAUDENKLO'S. 

